Composition for the oxidation dyeing of keratin fibres contains a 4-hydroxyindoline coupler at an acidic pH and dyeing process using this composition

ABSTRACT

PCT No. PCT/FR96/01472 Sec. 371 Date May 22, 1997 Sec. 102(e) Date May 22, 1997 PCT Filed Sep. 20, 1996 PCT Pub. No. WO97/11673 PCT Pub. Date Mar. 3, 1997The present invention relates to a ready-to-use composition for the oxidation dyeing of keratin fibers, in particular human keratin fibers such as the hair, this composition comprising, in an acidic medium (pH&lt;7), at least one oxidation base, in combination with 4-hydroxyindoline as coupler, and an oxidizing agent, as well as to the dyeing process using this composition.

The present invention relates to a ready-to-use composition for theoxidation dyeing of keratin fibres, in particular human keratin fibressuch as the hair, this composition comprising, in an acidic medium(pH<7), at least one oxidation base, in combination with4-hydroxyindoline as coupler, and an oxidizing agent, as well as to thedyeing process using this composition.

It is known to dye keratin fibres, and in particular human hair, withdye compositions containing oxidation dye precursors, in particularortho- or para-phenylenediamines and ortho- or para-aminophenols, whichare generally referred to as oxidation bases. Oxidation dye precursors,or oxidation bases, are colourless or weakly coloured compounds which,when combined with oxidizing products, may give rise to colouredcompounds and dyes by a process of oxidative condensation.

It is also known that the shades obtained with these oxidation bases maybe varied by combining them with couplers or coloration modifiers, thesebeing chosen in particular from aromatic meta-diamines,meta-aminophenols, meta-diphenols and certain indole or indolinecompounds.

The variety of molecules used as oxidation bases and couplers makes itpossible to obtain a wide range of colours.

The so-called "permanent" coloration obtained by means of theseoxidation dyes must moreover satisfy a certain number of requirements.Thus, it must have no toxicological drawbacks and it must allow shadesof the desired intensity to be obtained and have good resistance toexternal agents (light, inclement weather, washing, permanent waving,perspiration and rubbing).

The dyes must also allow grey hair to be covered and, lastly, they mustbe as unselective as possible, that is to say that they must allow thesmallest possible differences in coloration to be obtained over theentire length of the same keratin fibre, which may indeed be differentlysensitized (i.e. damaged) between its tip and its root.

The oxidation dyeing of the keratin fibres is generally carried out inalkaline medium. However, alkaline media have the drawback of causingappreciable degradation of the fibres. By way of example, French patentapplication FR 2,008,797 has already proposed compositions for theoxidation dyeing of keratin fibres in alkaline medium, comprising atleast one oxidation base and at least one indoline derivative ascoupler.

The oxidation dyeing of keratin fibres may also be performed in acidicmedium, in order to limit the degradation of the keratin fibres.However, the colorations obtained under these conditions are,unfortunately, generally less intense and not as fast as those obtainedin alkaline medium.

Now, the Applicant has just discovered that it is possible to obtainnovel dyes in acidic medium which are capable of giving rise to intensecolorations, which are quite unselective and which suitably withstandthe various attacks to which the hair may be subjected, by combining atleast one oxidation base, 4-hydroxyindoline and an oxidizing agent suchthat the resulting ready-to-use mixture has a pH below 7.

This discovery forms the basis of the present invention.

The first subject of the invention is thus a ready-to-use compositionfor the oxidation dyeing of keratin fibres, and in particular humankeratin fibres such as the hair, characterized in that it comprises, ina medium which is suitable for dyeing:

at least one oxidation base,

4-hydroxyindoline and/or at least one of the addition salts thereof withan acid, as coupler,

at least one oxidizing agent,

the pH of this ready-to-use composition being below 7.

The colorations obtained with the ready-to-use dye compositions inaccordance with the invention are at least as intense as, if not moreintense than, those of the prior art obtained with the same compositionsused at basic pH, and they are moreover of low selectivity and haveexcellent properties of resistance both to atmospheric agents such aslight and inclement weather and to perspiration and the varioustreatments to which the hair may be subjected (washing, permanentwaving).

The subject of the invention is also a process for the oxidation dyeingof keratin fibres using this ready-to-use dye composition.

The oxidation bases which may be used in the ready-to-use compositionsin accordance with the invention are preferably chosen frompara-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols,ortho-aminophenols and heterocyclic bases, and the addition saltsthereof with an acid.

The addition salts with an acid which may be used in the context of thedye compositions of the invention (oxidation bases and4-hydroxyindoline) are chosen in particular from the hydrochlorides,hydrobromides, sulphates and tartrates.

Among the para-phenylenediamines which may be used as oxidation bases inthe context of the ready-to-use compositions in accordance with theinvention, mention may be made in particular of the compoundscorresponding to formula (I) below, and the addition salts thereof withan acid: ##STR1## in which: R₁ represents a hydrogen atom or a C₁ -C₄alkyl, C₁ -C₄ monohydroxyalkyl, C₂ -C₄ polyhydroxyalkyl, (C₁-C₄)alkoxy(C₁ -C₄)alkyl, phenyl or 4'-aminophenyl radical,

R₂ represents a hydrogen atom or a C₁ -C₄ alkyl, C₁ -C₄ monohydroxyalkylor C₂ -C₄ polyhydroxyalkyl radical,

R₃ represents a hydrogen atom, a halogen atom such as a chlorine,bromine, iodine or fluorine atom or a C₁ -C₄ alkyl, C₁ -C₄monohydroxyalkyl or C₁ -C₄ hydroxyalkoxy radical,

R₄ represents a hydrogen atom or a C₁ -C₄ alkyl radical.

Among the para-phenylenediamines of formula (I) above, mention may bemade more particularly of para-phenylenediamine, para-toluylenediamine,2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine,N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine,4-amino-N,N-diethyl-3-methylaniline,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,4-amino-N,N-bis(β-hydroxyethyl)-3-methylaniline,4-amino-3-chloro-N,N-bis(β-hydroxyethyl)aniline,4-amino-N-(β-methoxyethyl)aniline,2-β-hydroxyethyl-para-phenylenediamine, 2-fluoropara-phenylenediamine,2-isopropyl-para-phenylenediamine,N-(β-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylenediamine,N,N-dimethyl-3-methyl-para-phenylenediamine,N-ethyl-N-(β-hydroxyethyl)-para-phenylenediamine,N-(β,γ-dihydroxypropyl)-para-phenylenediamine,N-(4'-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamineand 2-β-hydroxyethyloxy-para-phenylenediamine, and the addition saltsthereof with an acid.

Among the para-phenylenediamines of formula (I) above,para-phenylenediamine, para-toluylenediamine,2-isopropyl-para-phenylenediamine,2-β-hydroxyethyl-para-phenylenediamine,2-β-hydroxyethyloxy-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,4-amino-N-(β-methoxyethyl)aniline and 2-chloropara-phenylenediamine, andthe addition salts thereof with an acid, are most particularlypreferred.

Among the bis(phenyl)alkylenediamines which may be used as oxidationbases in the context of the ready-to-use compositions in accordance withthe invention, mention may be made in particular of the compoundscorresponding to formula (II) below, and the addition salts thereof withan acid: ##STR2## in which: Z₁ and Z₂, which may be identical ordifferent, represent a hydroxyl radical or a radical NHR₈ in which R₈represents a hydrogen atom or a C₁ -C₄ alkyl radical,

R₅ represents a hydrogen atom, a C₁ -C₄ alkyl, C₁ -C₄ monohydroxyalkylor C₂ -C₄ polyhydroxyalkyl radical or a C₁ -C₄ aminoalkyl radical inwhich the amino residue may be substituted,

R₆ and R₇, which may be identical or different, represent a hydrogen orhalogen atom or a C₁ -C₄ alkyl radical,

Y represents a radical taken from the group consisting of the followingradicals:

    --(CH.sub.2).sub.n -; --(CH.sub.2).sub.m -O--(CH.sub.2).sub.m -; --(CH.sub.2).sub.m -CHOH--(CH.sub.2).sub.m -

and ##STR3## in which n is an integer from 0 to 8 and m is an integerfrom 0 to 4.

Among the bis(phenyl)alkylenediamines of formula (II) above, mention maybe made more particularly ofN,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropanol,N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine,N,N'-bis(4-aminophenyl)tetramethylenediamine,N,N'-bis(β-hydroxyethyl)-N,N'-bis(4-aminophenyl)tetramethylenediamine,N,N'-bis(4-methylaminophenyl)tetramethylenediamine andN,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)ethylenediamine, andthe addition salts thereof with an acid.

Among these bis(phenyl)alkylenediamines of formula (II),N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropanol,or one of the addition salts thereof with an acid, is particularlypreferred.

Among the para-aminophenols which may be used as oxidation bases in thecontext of the ready-to-use compositions in accordance with theinvention, mention may be made in particular of the compoundscorresponding to formula (III) below, and the addition salts thereofwith an acid: ##STR4## in which: p1 R₉ represents a hydrogen atom or aC₁ -C₄ alkyl, C₁ -C₄ monohydroxyalkyl, (C₁ -C₄) alkoxy(C₁ -C₄) alkyl orC₁ -C₄ aminoalkyl radical,

R₁₀ represents a hydrogen or fluorine atom or a C₁ -C₄ alkyl, C₁ -C₄monohydroxyalkyl, C₂ -C₄ polyhydroxyalkyl, C₁ -c₄ aminoalkyl, C₁ -C₄cyanoalkyl or (C₁ -C₄)alkoxy-(C₁ -C₄)alkyl radical, it being understoodthat at least one of the radicals R₉ or R₁₀ represents a hydrogen atom.

Among the para-aminophenols of formula (III) above, mention may be mademore particularly of para-aminophenol, 4-amino-3-methylphenol,4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol,4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol,4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol and4-amino-2-(β-hydroxyethylaminomethyl)phenol, and the addition saltsthereof with an acid.

Among the ortho-aminophenols which may be used as oxidation bases in thecontext of the ready-to-use compositions of the invention, mention maybe made more particularly of 2-aminophenol, 2-amino-5-methylphenol,2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and the additionsalts thereof with an acid.

Among the heterocyclic bases which may be used as oxidation bases in thecontext of the ready-to-use compositions in accordance with theinvention, there may more particularly be mentioned pyridinederivatives, pyrimidine derivatives, pyrazole derivatives, and theaddition salts thereof with an acid.

Among the pyridine derivatives which may more particularly be mentionedare the compounds described, for example, in GB patents 1,026,978 and1,153,196, such as 2,5-diaminopyridine, and the addition salts thereofwith an acid.

Among the pyrimidine derivatives which may more particularly bementioned are the compounds described, for example, in German patent DE2,359,399 or Japanese patents JP 88-169,571 and JP 91-333,495, such as2,4,5,6-tetraaminopyrimidine and 4-hydroxy-2,5,6-triaminopyrimidine, andthe addition salts thereof with an acid.

Among the pyrazole derivatives which may more particularly be mentionedare the compounds described in patents DE 3,843,892 and DE 4,133,957 andpatent applications WO 94/08969 and WO 94/08970, such as4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole and4,5-diamino-1-(4'-chlorobenzyl)pyrazole, and the addition salts thereofwith an acid.

The oxidation base or bases preferably represent approximately from0.0005 to 12% by weight relative to the total weight of the dyecomposition, and even more preferably approximately from 0.005 to 6% byweight.

The 4-hydroxyindoline and/or the addition salts thereof with an acidpreferably represent(s) approximately from 0.0005 to 5% by weightrelative to the total weight of the dye composition, and even morepreferably approximately from 0.005 to 3% by weight.

According to an essential characteristic of the present invention, thepH of the ready-to-use dye composition in accordance with the inventionis below 7 and may preferably range from 3 to 6.9. It may be adjusted tothe desired value using acidifying or optionally basifying agents whichare commonly used in the dyeing of keratin fibres.

Among the acidifying agents which may be mentioned, by way of example,are inorganic or organic acids such as hydrochloric acid,orthophosphoric acid, carboxylic acids such as tartaric acid, citricacid and lactic acid, and sulphonic acids.

Among the basifying agents which may be mentioned, by way of example,are aqueous ammonia, alkaline carbonates, alkanolamines such as mono-,di- and triethanolamine and derivatives thereof, sodium hydroxide,potassium hydroxide and the compounds of formula (IV) below: ##STR5## inwhich R is a propylene residue optionally substituted with a hydroxylgroup or a C₁ -C₄ alkyl radical; R₁₁, R₁₂, R₁₃ and R₁₄, which may beidentical or different, represent a hydrogen atom or a C₁ -C₄ alkyl orC₁ -C₄ hydroxyalkyl radical.

The oxidizing agent present in the ready-to-use dye composition inaccordance with the invention may be chosen from the oxidizing agentsconventionally used in oxidation dyeing, and preferably from hydrogenperoxide, urea peroxide, alkali metal bromates and persalts such asperborates and persulphates. Hydrogen peroxide is particularlypreferred.

In addition to the dyes defined above, the ready-to-use dye compositionin accordance with the invention may also contain other couplers and/ordirect dyes, in particular to modify the shades or to enrich them withglints.

The appropriate medium for dyeing (or support) for the dye compositionsgenerally consists of water or of a mixture of water and at least oneorganic solvent to solubilize the compounds which would not besufficiently soluble in water. Organic solvents which may be mentioned,for example, are C₁ -C₄ lower alkanols such as ethanol and isopropanol;glycerol; glycols and glycol ethers such as 2-butoxyethanol, propyleneglycol, propylene glycol monomethyl ether, diethylene glycol monomethylether and monoethyl ether, as well as aromatic alcohols such as benzylalcohol or phenoxyethanol, similar products and mixtures thereof.

The solvents may be present in proportions preferably of approximatelybetween 1 and 40% by weight relative to the total weight of the dyecomposition, and even more preferably of approximately between 5 and 30%by weight.

The ready-to-use dye compositions in accordance with the invention mayalso include various adjuvants used conventionally in compositions fordyeing the hair, such as anionic, cationic, nonionic, amphoteric orzwitterionic surfactants or mixtures thereof, anionic, cationic,nonionic, amphoteric or zwitterionic polymers or mixtures thereof,inorganic or organic thickeners, antioxidants, penetration agents,sequestering agents, fragrances, buffers, dispersing agents,conditioners, film-forming agents, preserving agents and opacifyingagents.

Obviously, a person skilled in the art will take care to choose this orthese optional complementary compound(s) such that the advantageousproperties intrinsically associated with the ready-to-use composition inaccordance with the invention are not, or are substantially not,adversely affected by the addition or additions envisaged.

The ready-to-use dye compositions in accordance with the invention maybe in various forms, such as in the form of liquids, creams, gels or anyother form which is suitable for dyeing keratin fibres, and inparticular human hair.

Another subject of the invention is a process for dyeing keratin fibres,and in particular human keratin fibres such as the hair, using theready-to-use dye composition as defined above.

According to this process, at least one ready-to-use dye composition asdefined above is applied to the fibres and is left to stand on thefibres for 3 to 50 minutes approximately, preferably 5 to 30 minutesapproximately, after which the fibres are rinsed, optionally washed withshampoo, rinsed again and dried.

According to a preferred embodiment, the process includes a first stepconsisting in separately storing, on the one hand, a composition (A)comprising, in a medium which is suitable for dyeing, at least oneoxidation base and 4-hydroxyindoline and/or at least one of the additionsalts thereof with an acid, and, on the other hand, a composition (B)containing, in a medium which is suitable for dyeing, at least oneoxidizing agent, for example such as defined above, and then in mixingthem together at the time of use, before applying this mixture to thekeratin fibres, the pH of the compositions (A) and (B) being such thatafter mixing from 10 to 90% of composition (A) with 90 to 10% ofcomposition (B), the pH of the resulting mixture is below 7.

The pH of compositions (A) and (B) may be adjusted to the desired valueusing conventional acidifying or optionally basifying agents as definedabove.

Another subject of the invention is a multi-compartment dyeing device or"kit" or any other multi-compartment packaging system, a firstcompartment of which contains composition (A) as defined above and asecond compartment of which contains the oxidizing composition (B) asdefined above. These devices may be equipped with a means which makes itpossible to apply the desired mixture to the hair, such as the devicesdescribed in patent FR-2,586,913 in the name of the Applicant.

The examples which follow are intended to illustrate the inventionwithout, however, limiting the scope thereof.

EXAMPLES

The following dye compositions 1 (A) and 2 (A) in accordance with theinvention were prepared (contents in grams):

    ______________________________________                                        COMPOSITION           1 (A)     2 (A)                                         ______________________________________                                        Para-toluylenediamine 0.584                                                   2,6-Dimethyl-para-              0.627                                         phenylenediamine dihydrochloride                                              4-Hydroxyindoline     0.405     0.405                                         Common dye support (*)                                                                              (*)       (*)                                           Water qs              100 g     100 g                                         ______________________________________                                         (*) Common dye support:                                                       Oleyl alcohol polyglycerolated with 2 mol of glycerol 4.0 g                   Oleyl alcohol polyglycerolated with 4 mol of glycerol, containing 78% of      active materials (AM) 5.69 g AM                                               Oleic acid 3.0 g                                                              Oleylamine containing 2 mol of ethylene oxide, sold under the trade name      Ethomeen O12 by the company AKZO 7.0 g                                        Diethylaminopropyl laurylaminosuccinamate, sodium salt, containing 55% of     AM 3.0 g AM                                                                   Oleyl alcohol 5.0 g                                                           Oleic acid diethanolamide 12.0 g                                              Propylene glycol 3.5 g                                                        Ethyl alcohol 7.0 g                                                           Dipropylene glycol 0.5 g                                                      Propylene glycol monomethyl ether 9.0 g                                       Sodium metabisulphite in aqueous solution, containing 35% of AM 0.455 g A     Ammonium acetate 0.8 g                                                        Antioxidant, sequestering agent qs                                            Fragrance, preserving agent qs                                                Monoethanolamine qs pH 9.8                                               

Each dye composition 1 (A) and 2 (A) was mixed, at the time of use, withan equal weight amount of an oxidizing composition (B) consisting of20-volumes aqueous hydrogen peroxide solution (6% by weight) whose pHwas adjusted to between 1 and 1.5 with 2.5 g of orthophosphoric acid per100 g of aqueous hydrogen peroxide.

Each resulting composition had a pH below 7, and was applied for 30minutes to locks of permanent-waved grey hair containing 90% whitehairs. The locks of hair were then rinsed, washed with a standardshampoo and then dried.

Composition 1' (A) and 2' (A) were also prepared. These compositions 1'(A) and 2' (A) differed from the compositions 1 (A) and 2 (A) only inthat the monoethanolamine used to adjust the pH of the dye composition(see the common dye support defined above) was replaced with 10 g ofaqueous ammonia containing 20% of NH₃.

Each dye composition 1' (A) and 2' (A) was mixed, at the time of use,with an equal weight amount of an oxidizing composition (B') consistingof 20-volumes aqueous hydrogen peroxide solution (6% by weight) of pH 3.

Each resulting composition (not forming part of the invention) had a pHabove 7, and was applied for 30 minutes to locks of permanent-waved greyhair containing 90% white hairs. The locks of hair were then rinsed,washed with a standard shampoo and then dried.

The colour of the locks was then evaluated in the Munsell system using aMinolta CM 2002 calorimeter.

According to the Munsell notation, a colour is defined by the expressionHV/C in which the three parameters respectively denote the shade or Hue(H), the intensity or Value (V) and the purity or Chromaticity (C), theoblique line in this expression simply being a convention and notindicating a ratio.

The difference between the colour of the locks before and after dyeingwas calculated by applying the Nickerson formula:

    ΔE=0.4 C.sub.0 ΔH+6ΔV+3ΔC,

as described, for example, in "Couleur, Industrie et Technique"; pages14-17; vol. No. 5; 1978.

In this formula, ΔE represents the difference in colour between twolocks, ΔH, ΔV and ΔC represent the variation in absolute value of theparameters H, V and C, and C₀ represents the purity of the lock relativeto which it is desired to evaluate the colour difference.

ΔE thus reflects the intensity of the coloration obtained, which isproportionately greater the higher the value of ΔE.

The colour of the locks before dyeing was:

    4.3 Y 4.9/1.4

and thus

    C.sub.0 =1.4.

The results are given in the table below:

    ______________________________________                                                 pH of the                                                                     mixture   Colour of the                                                                             Intensity of the                               EXAMPLE  applied to                                                                              lock after  coloration                                      Composition!                                                                          the hair  dyeing      ΔH                                                                           ΔV                                                                          ΔC                                                                          ΔE                          ______________________________________                                        1 1 (A)! 6.9       7.8 YR 2.1/0.5                                                                            6.5  2.8 0.9 23.1                              1'  1' (A)!                                                                            9.9       5.2 YR 2.6/1.1                                                                            9.1  2.3 0.3 19.8                              2 2 (A)! 6.9       8.6 YR 2.3/0.3                                                                            5.7  2.6 1.1 22.1                              2' 2' (A)!                                                                             9.9       4.6 YR 2.7/0.8                                                                            9.7  2.2 0.6 20.4                              ______________________________________                                    

These results show that when the dyeing is performed with theready-to-use dye compositions in accordance with the invention, that isto say those in which the pH is below 7 (ready-to-use dye compositionsof Examples 1 and 2), it leads to colorations which are more intensethan those obtained with the ready-to-use dye compositions not formingpart of the invention (ready-to-use dye compositions of Examples 1' and2') which have a pH above 7.

I claim:
 1. A ready-to-use composition for the oxidation dyeing ofkeratin fibres, said composition comprising, in a medium which issuitable for dyeing, at least one oxidation base; 4-hydroxyindolineand/or at least one acid addition salt thereof as a coupler; and atleast one oxidizing agent, wherein the pH of said composition is below7.
 2. A composition according to claim 1, wherein said keratin fibresare human keratin fibres.
 3. A composition according to claim 1, whereinsaid at least one oxidation base is a para-phenylenediamine, abis(phenyl)alkylene-diamine, a para-aminophenol, an ortho-aminophenol, aheterocyclic base, or an acid addition salt of one of said compounds. 4.A composition according to claim 3, wherein said para-phenylenediamineis a compound of formula (I) or an acid addition salt thereof: ##STR6##in which: R₁ represents a hydrogen atom or a C₁ -C₄ alkyl, C₁ -C₄monohydroxyalkyl, C₂ -C₄ polyhydroxyalkyl, (C₁ -C₄)alkoxy(C₁ -C₄)alkyl,phenyl or 4'-aminophenyl radical;R₂ represents a hydrogen atom or a C₁-C₄ alkyl, C₁ -C₄ monohydroxyalkyl or C₂ -C₄ polyhydroxyalkyl radical;R₃ represents a hydrogen atom, a halogen atom, or a C₁ -C₄ alkyl, C₁ -C₄monohydroxyalkyl or C₁ -C₄ hydroxyalkoxy radical; and R₄ represents ahydrogen atom or a C₁ -C₄ alkyl radical.
 5. A composition according toclaim 4, wherein said halogen atom is a chlorine, bromine, iodine orfluorine atom.
 6. A composition according to claim 4, wherein saidpara-phenylenediamine of formula (I) is para-phenylenediamine,para-toluylenediamine, 2-chloropara-phenylenediamine,2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine,2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine,N,N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine,N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,4-amino-N,N-bis(β-hydroxyethyl)-3-methylaniline, 4-amino-3-chloro-N,N-bis(β-hydroxyethyl)-aniline, 4-amino-N-(β-methoxyethyl)aniline,2-β-hydroxyethyl-para-phenylenediamine, 2-fluoropara-phenylenediamine,2-isopropyl-para-phenylenediamine,N-(β-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylenediamine,N,N-dimethyl-3-methyl-para-phenylenediamine,N-ethyl-N-(β-hydroxyethyl)-para-phenylenediamine,N-(β,γ-dihydroxypropyl)-para-phenylenediamine,N-(4'-aminophenyl)-para-phenylene-diamine,N-phenyl-para-phenylenediamine,2-β-hydroxyethyloxy-para-phenylenediamine, or an acid addition salt ofone of said compounds.
 7. A composition according to claim 6, whereinsaid para-phenylenediamine of formula (I) is para-phenylenediamine,para-toluylenediamine, 2-isopropyl-para-phenylenediamine,2-β-hydroxyethyl-para-phenylenediamine,2-β-hydroxyethyloxy-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,4-amino-N-(β-methoxyethyl)aniline, 2-chloropara-phenylenediamine, or anacid addition salt of one of said compounds.
 8. A composition accordingto claim 3, wherein said bis(phenyl)alkylenediamine is a compound offormula (II) or an acid addition salt thereof: ##STR7## in which: Z₁ andZ₂, which may be identical or different, represent a hydroxyl radical ora radical NHR₈ in which R₈ represents a hydrogen atom or a C₁ -C₄ alkylradical;R₅ represents a hydrogen atom, a C₁ -C₄ alkyl, C₁ -C₄monohydroxyalkyl or C₂ -C₄ polyhydroxyalkyl radical or a C₁ -C₄aminoalkyl radical in which the amino residue is optionally substituted;R₆ and R₇, which may be identical or different, represent a hydrogen orhalogen atom or a C₁ -C₄ alkyl radical; Y represents a radical selectedfrom the group consisting of the following radicals:

    --(CH.sub.2).sub.n -; --(CH.sub.2).sub.m -O--(CH.sub.2).sub.m -; --(CH.sub.2).sub.m -CHOH--(CH.sub.2).sub.m -

and ##STR8## in which n is an integer ranging from 0 to 8 and m is aninteger ranging from 0 to
 4. 9. A composition according to claim 8,wherein said bis(phenyl)alkylenediamine is aN,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropanol,N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine,N,N'-bis(4-aminophenyl)tetramethylenediamine,N,N'-bis(β-hydroxyethyl)-N,N'-bis(4-aminophenyl)-tetramethylenediamine,N,N'-bis(4-methylaminophenyl)tetramethylenediamine,N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)ethylenediamine, or anacid addition salt of one of said compounds.
 10. A composition accordingto claim 9, wherein said bis(phenyl)alkylenediamine isN,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropanol oran acid addition salt thereof.
 11. A composition according to claim 3,wherein said para-aminophenol is a compound of formula (Ill) or an acidaddition salt thereof: ##STR9## in which: R₉ represents a hydrogen atomor a C₁ -C₄ alkyl, C₁ -C₄ monohydroxyalkyl, (C₁ -C₄)alkoxy(C₁ -C₄)alkylor C₁ -C₄ aminoalkyl radical; andR₁₀ represents a hydrogen or fluorineatom or a C₁ -C₄ alkyl, C₁ -C₄ monohydroxyalkyl, C₂ -C₄polyhydroxyalkyl, C₁ -C₄ aminoalkyl, C₁ -C₄ cyanoalkyl or (C₁-C₄)alkoxy-(C₁ -C₄)alkyl radical; wherein at least one of the radicalsR₉ or R₁₀ represents a hydrogen atom.
 12. A composition according toclaim 11, wherein said para-aminophenol is para-aminophenol,4-amino-3-methylphenol, 4-amino-3-fluorophenol,4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol,4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol,4-amino-2-aminomethylphenol,4-amino-2-(β-hydroxyethylaminomethyl)phenol, or an acid addition salt ofone of said compounds.
 13. A composition according to claim 3, whereinsaid ortho-aminophenol is 2-aminophenol, 2-amino-5-methylphenol,2-amino-6-methylphenol, 5-acetamido-2-aminophenol, or an acid additionsalt of one of said compounds.
 14. A composition according to claim 3,wherein said heterocyclic base is a pyridine derivative, a pyrimidinederivative, a pyrazole derivative, or an acid addition salt of one ofsaid compounds.
 15. A composition according to claim 14, wherein saidheterocyclic base is 2,4,5,6-tetraaminopyrimidine, 2,5-diaminopyridine,4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole,4,5-diamino-1-(4'-chlorobenzyl)-pyrazole,4-hydroxy-2,5,6-triaminopyrimidine, or an acid addition salt of one ofsaid compounds.
 16. A composition according to claim 1, wherein said atleast one acid addition salt is a hydrochloride, hydrobromide, sulphateor tartrate.
 17. A composition according to claim 1, wherein said atleast one oxidation base represents from 0.0005 to 12% by weightrelative to the total weight of the dye composition.
 18. A compositionaccording to claim 17, wherein said at least one oxidation baserepresents from 0.005 to 6% by weight relative to the total weight ofthe dye composition.
 19. A composition according to claim 1, whereinsaid 4-hydroxyindoline and/or said at least one acid addition saltthereof represents from 0.0005 to 5% by weight relative to the totalweight of the dye composition.
 20. A composition according to claim 19,wherein said 4-hydroxyindoline and/or said at least one acid additionsalt thereof represents from 0.005 to 3% by weight relative to the totalweight of the dye composition.
 21. A composition according to claim 1,wherein said pH ranges from 3 to 6.9.
 22. A composition according toclaim 1, wherein said at least one oxidizing agent is hydrogen peroxide,urea peroxide, an alkali metal bromate or a persalt.
 23. A compositionaccording to claim 22, wherein said persalt is a perborate or apersulphate.
 24. A process for dyeing keratin fibres, said processcomprising applying at least one ready-to-use dye composition accordingto claim 1 to said fibres.
 25. A process according to claim 24, whereinsaid keratin fibres are human keratin fibres.
 26. A process according toclaim 25, wherein said human keratin fibres are hair.
 27. A processaccording to claim 24, said process comprising:separately storing acomposition (A) and a composition (B), said composition (A) comprising,in a medium suitable for dyeing, at least one oxidation base and4-hydroxyindoline and/or at least one acid addition salt thereof, saidcomposition (B) comprising, in a medium suitable for dyeing, at leastone oxidizing agent; combining, just prior to the time of application,from 10 to 90% of said composition (A) with from 10 to 90% of saidcomposition (B) to form a mixture, said mixture having a pH below 7; andapplying said mixture to said keratin fibres.
 28. A multi-compartmentdyeing device, which comprises at least two compartments, wherein afirst compartment contains a composition (A) comprising, in a mediumsuitable for dyeing, at least one oxidation base and 4-hydroxyindolineand/or at least one acid addition salt thereof, and a second compartmentcontains a composition (B) comprising, in a medium suitable for dyeing,at least one oxidizing agent, said compositions (A) and (B) having pH'ssuch that when combining 10 to 90% of said composition (A) with from 10to 90% of said composition (B) to form a mixture, said mixture has a pHbelow 7.